CN102290599A - Noaqueous electrolyte and nonaqueous electrolyte battery - Google Patents

Noaqueous electrolyte and nonaqueous electrolyte battery Download PDF

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CN102290599A
CN102290599A CN2011101561828A CN201110156182A CN102290599A CN 102290599 A CN102290599 A CN 102290599A CN 2011101561828 A CN2011101561828 A CN 2011101561828A CN 201110156182 A CN201110156182 A CN 201110156182A CN 102290599 A CN102290599 A CN 102290599A
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nonaqueous electrolyte
salt
compound
battery
heteropoly
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山田一郎
齐藤俊介
渡边春夫
洼田忠彦
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Sony Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/02—Lithium compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
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    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a noaqueous electrolyte and a nonaqueous electrolyte battery. Concretely, the invention relates to a nonaqueous electrolyte, including: a nonaqueous solvent; an electrolyte salt; an imide salt; and at least one of a heteropolyacid and a heteropolyacid compound. The nonaqueous electrolyte battery in the invention can inhibit reaction between an electrode and the noaqueous electrolyte during charging and discharging, improve circulating characteristic under high-temperature environment, and inhibit generation of gas during continuous charging.

Description

Nonaqueous electrolyte and nonaqueous electrolyte battery
Technical field
The present invention relates to nonaqueous electrolyte and battery, particularly, relate to the nonaqueous electrolyte that comprises organic solvent and electrolytic salt, and the nonaqueous electrolyte battery that utilizes this nonaqueous electrolyte.
Background technology
For littler, lighter and more long-life portable electron device, has strong demand as the integrated VTR of the camera that becomes recent years general (video tape recorder), cellular phone and laptop PC.In this respect, developed battery, particularly light and secondary cell that high-energy-density can be provided is as the compact power of such electronic installation.
Especially, utilize the embedding of lithium (Li) and take off that embedding is used to charge and the secondary cell (lithium rechargeable battery) of exoelectrical reaction, because they can provide than such as the higher energy density of other rechargeable nonaqueous electrolytic batteries of excide battery and nickel-cadmium cell, so dropped in the practical application widely.Lithium rechargeable battery comprises positive pole, negative pole and electrolyte.
Outside (packing) utilizes the lamination battery of aluminium lamination press mold light, and therefore has extra high energy density.As a kind of distortion of such lamination battery, the lamination macromolecule battery also is widely used, because the distortion of this lamination battery can be suppressed by the high molecular swelling of utilizing nonaqueous electrolytic solution.
Yet, because this lamination battery has soft outer packaging, so this battery is tending towards the swelling along with the gas that produces at inside battery during initial charge and high-temperature storage.In JP-A-2006-86058 (patent documentation 1), solved this problem.In this patent disclosure, with halogenated cyclic carbonic ester such as carbonic acid fluorine second diester or have the cyclic carbonate ester of C-C multikey such as adding in the nonaqueous electrolyte of vinylene carbonate, thereby suppress reaction or other forms of interaction between negative electrode active material and the nonaqueous electrolyte, and therefore suppress the battery swelling during the initial charge.Yet these reactive cyclic carbonates can not suppress high temperature between the operating period, especially the battery swelling during the trickle charge.
JP-A-2001-297765 (patent documentation 2) has described a kind of high-capacity lithium-ion secondary cell, and it uses imide salt (imide salts, imide salt) electrolyte and has excellent charging and discharging circulation (characteristic).
Summary of the invention
Can not suppress battery swelling during high temperature the battery swelling between the operating period, particularly trickle charge as the utilization of the reactive cyclic carbonate of being instructed in the patent documentation 1.Reduced discharge capacity as the electrolytical utilization that has imide salt in the patent documentation 2,, therefore can not provide sufficient battery behavior fully because imide salt and negative electrode active material react.
Therefore, there are needs even also have the nonaqueous electrolyte battery of the battery behavior of improvement when under hot environment, using.
According to an embodiment of the invention, a kind of nonaqueous electrolyte is provided, it comprises at least a in nonaqueous solvents, electrolytic salt, imide salt and heteropoly acid (heteropolyacid) and the heteropoly compound.
According to another implementation of the invention, non-a kind of Water-Electrolyte battery is provided, it comprises positive pole, negative pole and nonaqueous electrolyte, come from imide salt and be formed on coating in anodal lip-deep at least a portion wherein anodal comprising, and wherein negative pole is included in the gel coat (gel coating) that forms at least a portion on the negative terminal surface, this gel coat comes from least a in (originating from) heteropoly acid and the heteropoly compound, and comprise and contain one or more multielement (coordination atoms, polyelement or addenda atom) noncrystal polyacid (multiple-metal oxygen-containing acid, polyacid or polyoxometalate) and/or multi-acid salt.
Imide salt in the preferred embodiment of the present invention is by following formula (I) or (II) expression.
(C mF 2m+1SO 2)(C nF 2n+1SO 2)NLi ...(I)，
Wherein, m and n are the integers more than 0
Figure BDA0000067554070000031
Wherein, R represents the straight or branched perfluorinated alkylidene (perfluor alkylene, perfluoroalkylene group) of 2 to 4 carbon atoms.
Heteropoly acid and heteropoly compound in the preferred embodiment of the present invention are represented by following formula (III) to (VI).
HxAy[BD 6O 24]·zH 2O ...(III)
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt (phosphonium salt), B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), one or more elements in rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤8 respectively, 0≤y≤8 and 0≤z≤50, wherein, at least one among x and the y is not 0;
HxAy[BD 12O 40]·zH 2O ...(IV)
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤4,0≤y≤4 and 0≤z≤50 respectively, wherein, at least one among x and the y is not 0;
HxAy[B 2D 18O 62]·zH 2O ...(V)
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤8,0≤y≤8 and 0≤z≤50 respectively, wherein, at least one among x and the y is not 0;
HxAy[B 5D 30O 110]·zH 2O ...(VI)
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤15,0≤y≤15 and 0≤z≤50 respectively, wherein, at least one among x and the y is not 0.
In embodiments of the present invention, nonaqueous electrolyte comprises at least a in imide salt and heteropoly acid and the heteropoly compound.By this way, on positive pole, form the coating that comes from imide salt, and on negative pole, form at least a coating that comes from heteropoly acid and the heteropoly compound.Reaction between both positive and negative polarity and the nonaqueous electrolyte can utilize the coating that forms on both positive and negative polarity to suppress.And the negative pole coating can prevent that imide salt from taking place to decompose and prevent that it from suppressing the performance of negative electrode active material near negative pole.
Embodiments of the present invention provide and have suppressed to decompose the gas generation that causes by nonaqueous electrolyte, and the approach of the battery swelling relevant with such gas generation.The deterioration that can also suppress the battery behavior between the following operating period of hot environment.
Description of drawings
Fig. 1 shows the cutaway view according to the representative configuration of the nonaqueous electrolyte battery of one embodiment of the present invention.
Fig. 2 is the part amplification view of the rolled electrode unit shown in Fig. 1.
Fig. 3 is the SEM photographic view according to the negative terminal surface of an embodiment of the invention.
Fig. 4 is illustrated in existence by on the sedimentary negative terminal surface of adding silico-tungstic acid to battery system and forming, an example of the secondary ion spectrum that obtains by time of flight secondary ion massspectrometry (ToF-SIMS).
Fig. 5 is illustrated in from existing by adding to battery system on the sedimentary negative terminal surface that silico-tungstic acid forms, an example of the W-O key radial structure function that obtains by the Fourier transform that absorbs the spectrogram that fine structure (XAFS) analyzes from X ray.
Fig. 6 shows the decomposition diagram of the representative configuration of nonaqueous electrolyte battery according to another implementation of the invention.
Fig. 7 is the cutaway view of the rolled electrode unit of Fig. 6 I-I intercepting along the line.
Fig. 8 is the cutaway view of expression according to the another kind of representative configuration of the nonaqueous electrolyte battery of one embodiment of the present invention.
Fig. 9 shows the perspective view according to the another kind of representative configuration of the nonaqueous electrolyte battery of one embodiment of the present invention.
Embodiment
Below with reference to accompanying drawing embodiments of the present invention are described.To be described in the following sequence.
1. first execution mode (example that comprises imide salt and heteropoly compound nonaqueous electrolyte of the present invention)
2. second execution mode (utilizing the example of cylindrical nonaqueous electrolyte battery)
3. the 3rd execution mode (utilizing the example of lamination membranous type nonaqueous electrolyte battery)
4. the 4th execution mode (utilizing the example of lamination membranous type nonaqueous electrolyte battery)
5. the 5th execution mode (utilizing the example of rectangle nonaqueous electrolyte battery)
6. the 6th execution mode (utilizing the example of the nonaqueous electrolyte battery of lamination electrode unit)
7. other execution modes
1. first execution mode
The nonaqueous electrolytic solution of first embodiment of the invention is described below.The nonaqueous electrolytic solution of first embodiment of the invention is used for electrochemical appliance, for example battery.This nonaqueous electrolytic solution comprise nonaqueous solvents, electrolytic salt and imide salt and heteropoly compound the two.This electrolytic salt, imide salt and heteropoly compound are dissolved in the solvent.
(1-1) imide salt
The imide salt of embodiment of the present invention is by following formula (I) or (II) expression.
(C mF 2m+1SO 2)(C nF 2n+1SO 2)NLi ...(I)
In the formula, m and n are the integers more than 0.
Figure BDA0000067554070000061
In the formula, R represents the straight or branched perfluorinated alkylidene of 2 to 4 carbon atoms.
Under formula (I) or imide salt (II) were included in situation in the nonaqueous electrolyte, the imide salt anion with fluorin radical was adsorbed on the electrode, particularly on anodal surface, and formed coating.Think that this coating has suppressed the particularly reaction between hot environment bottom electrode and nonaqueous electrolytic solution, and reduced thus at the gas of high temperature between the operating period and produce and reduce the battery swelling.Can also prevent the deterioration of the battery behavior between the continuous operating period under the hot environment.
Yet imide salt is problematic when using separately, because its reactivity with negative electrode active material makes charging and discharge difficult, and has reduced discharge capacity.Think that exist jointly (co-presence) of heteropoly compound prevented that the mobile of lithium ion from being suppressed by the decomposition of imide salt itself.This thinks that this SEI comes from heteropoly acid and forms on negative pole by charging and discharge, allows the embedding of lithium ion and takes off embedding owing to be called the metastable structure of the stable coatings of SEI (solid electrolyte interface) in initial the use.
Therefore, utilize heteropoly compound, can improve the battery behavior under the hot environment, do not reduce battery capacity and capability retention (percentage remaining capacity) simultaneously by the imide salt that in common scope, uses.
The example of the chain imide salt of formula (I) expression comprises two (fluorine sulphonyl) imines lithiums (lithium bis (fluorosulfonyl) imide), two (fluoroform sulphonyl) imines lithium, two (five fluorine second sulphonyl) imines lithium, two (seven fluorine, third sulphonyl) imines lithium, two (nine fluorine fourth sulphonyl) imines lithium, (fluoroform sulphonyl) (five fluorine second sulphonyl) imines lithium, (fluoroform sulphonyl) (seven fluorine, third sulphonyl) imines lithium and (fluoroform sulphonyl) (nine fluorine fourth sulphonyl) imines lithium.
The example of the cyclic imide salt of formula (II) expression comprises hexafluoroethane-1,2-disulfonyl imines lithium (perfluoroethane-1,2-disulfonylimide lithium), hexafluoroethane-1,3-disulfonyl imines lithium and hexafluoroethane-1,4-disulfonyl imines lithium.
Can make up the two or more compound that utilizes the compound selection that is selected from formula (I) and/or formula (II).
Imide salt content in the nonaqueous electrolyte is preferably below the above 1.0mol/kg of 0.01mol/kg, more preferably below the above 0.2mol/kg of 0.025mol/kg.When imide salt content is too small, can not suppress side reaction.Too high imide salt content neither be preferred, because it reduces battery capacity.
In embodiments of the present invention, can add than the more imide salt of prior art.The adding imide salt significantly improves the battery behavior under the hot environment.Yet, because imide salt reduces discharge capacity in the decomposition at negative pole place, so may be only mix imide salt with the amount of this problem of minimizing the negative pole place.Therefore on the other hand, in embodiments of the present invention, use heteropoly compound together, and do not need the problem of considering that the imide salt at the negative pole place decomposes, thereby allow to be enough to providing the amount of effect that imide salt is added in the battery system at negative pole.
(1-2) heteropoly acid and heteropoly compound
The heteropoly acid and the heteropoly compound of embodiments of the present invention are formed by heteropoly acid, and wherein heteropoly acid is the condensation product of two or more oxyacid (oxoacid).The polyacid ion of heteropoly acid and heteropoly compound preferably has the structure that is easy to dissolve in battery solvent, as Anderson structure, Keggin structure, Dawson structure and Preyssler structure.
The heteropoly acid that forms heteropoly acid and heteropoly compound is to comprise the polyatom (hetero-atom that is selected from element set (a), polyatom or heteroatom) heteropoly acid, perhaps comprise the polyatom that is selected from element set (a) and wherein this polyatomic part be selected from the heteropoly acid of at least a replacement of element set (b).
Element set (a): Mo, W, Nb, V
Element set (b): Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Tc, Rh, Cd, In, Sn, Ta, Re, Tl, Pb
And heteropoly acid and/or heteropoly compound are to comprise heteroatomic heteropoly acid and/or the heteropoly compound that is selected from element set (c); Perhaps comprise the hetero-atom that is selected from element set (c) and wherein this heteroatomic part be selected from heteropoly acid and/or the heteropoly compound that at least a element of element set (d) replaces.
Element set (c): B, Al, Si, P, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, As
Element set (d): H, Be, B, C, Na, Al, Si, P, S, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Zr, Rh, Sn, Sb, Te, I, Re, Pt, Bi, Ce, Th, U, Np
The example of the heteropoly acid that comprises in the heteropoly compound that uses in the embodiment of the present invention comprises assorted many wolframic acids such as phosphotungstic acid (phosphotungstic acid) and silico-tungstic acid (silicotungstic acid), and heteropoly molybdic acid such as phosphomolybdic acid (phosphomolybdic acid) and silicomolybdic acid (silicomolybdic acid).Comprise that the example more than a kind of material of multielement comprises phosphovanadomolybdic acid (phosphovanadomolybdic acid), phosphotungstomolybdic acid (phosphotungstomolybdic acid), silicon vanadium molybdic acid (silicovanadomolybdic acid) and silicon tungsten molybdic acid (silicotungstomolybdic acid).
The heteropoly compound that uses in the embodiment of the present invention is to be selected from least a in the compound of (VI) of following formula (III).
Formula (III): Anderson structure
HxAy[BD 6O 24]·zH 2O
In the formula, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt (phosphonium salt).B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge).D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl).Variable x, y and z satisfy 0≤x≤8,0≤y≤8 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0.
Formula (IV): Keggin structure
HxAy[BD 12O 40]·zH 2O
In the formula, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt.B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge).D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl).Variable x, y and z satisfy 0≤x≤4,0≤y≤4 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0.
Formula (V): Dawson structure
HxAy[B 2D 18O 62]·zH 2O
In the formula, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt.B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge).D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl).Variable x, y and z satisfy 0≤x≤8,0≤y≤8 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0.
Formula (VI): Preyssler structure
HxAy[B 5D 30O 110]·zH 2O
In the formula, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt.B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge).D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl).Variable x, y and z satisfy 0≤x≤15,0≤y≤15 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0.
In nonaqueous electrolyte, comprise formula (III) under the situation of the heteropoly acid of (VI) and/or heteropoly compound,, on electrode surface, particularly on negative terminal surface, form stable coating (SEI) by charging in the initial use and discharge.Because come from heteropoly compound and can embed the lithium ion permeability that has excellence with the coating of removal lithium embedded, so think that this coating reduces gas at high temperature and produces between the operating period, suppress the reaction between electrode and the nonaqueous electrolytic solution simultaneously, and can not damage cycle characteristics.And, as mentioned above, think that also this coating suppresses the reaction between imide salt and the negative electrode active material, and prevent that moving of lithium ion from being stoped by the decomposition of imide salt.
Heteropoly compound preferably has cation, for example Li +, Na +, K +, Rb +, Cs +, R 4N +And R 4P +(wherein R is the alkyl of H or 10 following carbon atoms).Cation is preferably Li +, tetra-n-butyl ammonium or tetra-n-butyl phosphine.
The example of such heteropoly compound comprises assorted many wolframic acids compound, as silicotungstic sodium, sodium phosphotungstate, ammonium phosphotungstate and silico-tungstic acid four (tetra-n-butyl phosphine) (tetra-tetra-n-butyl phosphonium silicotungstate).Other examples of heteropoly compound comprise the heteropoly molybdic acid compound, as sodium phosphomolybdate, ammonium phosphomolybdate and phosphomolybdic acid three (tetra-n-butyl ammonium) (tri-tetra-n-butyl ammonium phosphomolybdate).Comprise that examples for compounds more than a kind of multielement comprises the material such as phosphotungstomolybdic acid three (tetra-n-butyl ammonium).Heteropoly acid and heteropoly compound can be used as two or more mixtures and use.This heteropoly acid and heteropoly compound are easy to be dissolved in the solvent, and because the stability in battery, so be not easy to for example by causing adverse effect with the other materials reaction.
In embodiments of the present invention, can utilize at least a in polyacid (polyacid) and the polyacid compound.The polyacid ion of polyacid and polyacid compound preferably has the structure that is easy to dissolve in battery solvent, as Anderson structure, Keggin structure, Dawson structure and Preyssler structure.Except heteropoly compound, different polyacid (isopolyacid) compound also can be used as polyacid compound.The weight of every interpolation, different polyacid compound is effective not as heteropoly compound.Yet, because the low solubility in polar solvent so when being used for anodal and negative pole, different polyacid compound provides excellent coating characteristic, comprises coating viscoplasticity and anti-deterioration in time, and therefore sees that from industrial point of view different polyacid is useful.
Situation as heteropoly compound, the polyacid compound that uses in the embodiment of the present invention is to comprise the polyatomic polyacid compound that is selected from element set (a), or comprises the polyacid compound of at least a replacement that the polyatom that is selected from element set (a) and some polyatoms are selected from element set (b).
Element set (a): Mo, W, Nb, V
Element set (b): Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Tc, Rh, Cd, In, Sn, Ta, Re, Tl, Pb
The example of the polyacid that comprises in the polyacid compound that uses in the embodiment of the present invention comprises wolframic acid (VI) and molybdic acid (VI).Concrete example comprises tungstic acid anhydride (tungstic anhydride), molybdic acid anhydride (molybdenum anhydride) and their hydrate.The example of hydrate comprises positive wolframic acid (ortho-tungstic acids) (H 2WO 4), a tungstic acid hydrate (monohydrate) (WO particularly 3H 2O); And positive molybdic acid, more specifically two molybdic acid hydrate (H 4MoO 5, H 2MoO 4H 2O, MoO 32H 2O) and a molybdic acid hydrate (MoO 3H 2O).Also may use the tungstic acid anhydride (WO that has than the hydrogen content of the different polyacid of aforementioned hydrate such as metatungstic acid (meta-tungstic acid) and para-tungstic acid (para-tungstic acid) lower (finally being zero) 3), or have molybdic acid anhydride (MoO than the hydrogen content of metamolybdic acid, para-molybdic acid lower (finally being zero) 3).
Nonaqueous electrolyte comprises heteropoly acid or the heteropoly compound of formula (III) to (VI).Also can be used in combination the formula of being selected from (III) two or more in the heteropoly acid of (VI) or the heteropoly compound.Especially preferably the heteropoly compound that structure is not contained proton or water adds in the nonaqueous electrolyte, because this feasible water content that might control in the nonaqueous electrolytic solution, and suppress free acid (free acid) generation, and no matter the amount of the heteropoly compound that adds.
The heteropoly acid in the nonaqueous electrolytic solution and the content of heteropoly compound, the angle of battery swelling after the initial charge, be preferably below the above 3.0 weight % of 0.01 weight %, the angle of battery swelling after initial charge and after the high-temperature storage is more preferably below the above 2.0 weight % of 0.05 weight %.When heteropoly acid and heteropoly compound content were too small, SEI formed and becomes insufficient, and was difficult to obtain to add the effect of heteropoly compound.Excessive content neither be preferred, because reaction makes irreversible capacity too big, and reduces battery capacity.
(1-3) be used to add the structure of the nonaqueous electrolyte of imide salt and heteropoly compound
Electrolytic salt
Electrolytic salt comprises that for example, one or more light metal salt are as lithium salts.The example of lithium salts comprises lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4), lithium perchlorate (LiClO 4), hexafluoroarsenate lithium (LiAsF 6), tetraphenyl lithium borate (LiB (C 6H 5) 4), methanesulfonic acid lithium (LiCH 3SO 3), trifluoromethanesulfonic acid lithium (LiCF 3SO 3), tetrachloro-lithium aluminate (LiAlCl 4), hexafluorosilicic acid two lithium (Li 2SiF 6), lithium chloride (LiCl) and lithium bromide (LiBr).Be selected from lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4), lithium perchlorate (LiClO 4) and hexafluoroarsenate lithium (LiAsF 6) at least a be preferred, lithium hexafluoro phosphate (LiPF wherein 6) be preferred.Preferred these are because they reduce the ability of the resistance of nonaqueous electrolyte.Utilize lithium hexafluoro phosphate (LiPF 6) and LiBF4 (LiBF 4) be particularly preferred, because this provides strong effect.
Nonaqueous solvents
Examples of non-aqueous comprises ethylene carbonate (EC), propylene carbonate (PC), carbonic acid fourth diester (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), gamma-butyrolacton, gamma-valerolactone, 1, the 2-dimethoxy-ethane, oxolane, the 2-methyltetrahydrofuran, oxinane, 1, the 3-dioxolanes, the 4-methyl isophthalic acid, the 3-dioxolanes, 1, the 3-diox, 1, the 4-diox, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate (isomethyl butyrate), methyl trimethylacetate, tri-methyl ethyl acetate, acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, the 3-methoxypropionitrile, N, dinethylformamide, the N-methyl pyrrolidone, the N-methyl oxazolidinone, N, N '-dimethyl-imidazolinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate and methyl-sulfoxide.These provide excellent capacity, excellent cycle characteristics and excellent storage characteristics in the battery that utilizes nonaqueous electrolyte and other electrochemical appliances.These can use separately or use as two or more mixtures.
Preferably, the solvent of use comprises and is selected from least a in ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and the methyl ethyl carbonate (EMC).Preferred these are because they provide the ability of abundant effect.In this case, preferred use high viscosity (high dielectric property) solvent (for example, relative dielectric constant ε 〉=30) for example ethylene carbonate and propylene carbonate, as with low viscosity solvent (for example, the mixture of dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate for example of viscosity≤1mPas).Utilize such mixture to improve the disassociation and the ionic mobility of electrolytic salt, and therefore stronger effect is provided.
Nonaqueous solvents can contain by following formula (VII) or (VIII) expression cyclic carbonate.Be selected from two or more can being used in combination in formula (VII) and the compound (VIII).
In this formula, R1 to R4 is hydrogen group, halogen group, alkyl or haloalkyl, and among the R1 to R4 at least one is halogen group or haloalkyl.
Figure BDA0000067554070000132
In this formula, R5 and R6 are hydrogen group or alkyl.
Example by the halogen-containing cyclic carbonate of formula (VII) expression comprises 4-fluoro-1,3-dioxolanes-2-ketone, 4-chloro-1,3-dioxolanes-2-ketone, 4,5-two fluoro-1,3-dioxolanes-2-ketone, tetrafluoro-1,3-dioxolanes-2-ketone, 4-chloro-5-fluoro-1,3-dioxolanes-2-ketone, 4,5-two chloro-1,3-dioxolanes-2-ketone, tetrachloro-1,3-dioxolanes-2-ketone, 4,5-bis trifluoromethyl-1,3-dioxolanes-2-ketone, the 4-Trifluoromethyl-1,3-dioxolanes-2-ketone, 4,5-two fluoro-4,5-dimethyl-1,3-dioxolanes-2-ketone, 4,4-two fluoro-5-methyl isophthalic acids, 3-dioxolanes-2-ketone, 4-ethyl-5,5-two fluoro-1,3-dioxolanes-2-ketone, 4-fluoro-5-Trifluoromethyl-1,3-dioxolanes-2-ketone, 4-methyl-5-Trifluoromethyl-1,3-dioxolanes-2-ketone, 4-fluoro-4,5-dimethyl-1,3-dioxolanes-2-ketone, 5-(1,1-two fluoro ethyls)-4,4-two fluoro-1,3-dioxolanes-2-ketone, 4,5-two chloro-4,5-dimethyl-1,3-dioxolanes-2-ketone, 4-ethyl-5-fluoro-1,3-dioxolanes-2-ketone, 4-ethyl-4,5-two fluoro-1,3-dioxolanes-2-ketone, 4-ethyl-4,5,5-three fluoro-1,3-dioxolanes-2-ketone and 4-fluoro-4-methyl isophthalic acid, 3-dioxolanes-2-ketone.These can use separately or use as two or more mixtures.Among this, 4-fluoro-1,3-dioxolanes-2-ketone and 4,5-two fluoro-1,3-dioxolanes-2-ketone are preferred, because their easy acquisitions, and strong effect can be provided.
Example by the cyclic carbonate that contains unsaturated bond of formula (VIII) expression comprises vinylene carbonate (1,3-dioxole-2-ketone), carbonic acid methyl vinylene (4-methyl isophthalic acid, 3-dioxole-2-ketone), carbonic acid ethyl vinylene (4-ethyl-1,3-dioxole-2-ketone), 4,5-dimethyl-1,3-dioxole-2-ketone, 4,5-diethyl-1,3-dioxole-2-ketone, 4-fluoro-1,3-dioxole-2-ketone and 4-Trifluoromethyl-1,3-dioxole-2-ketone.These can use separately or use as two or more mixtures.Among this, vinylene carbonate is preferred, because it is easy to obtain, and can provide strong effect.
Macromolecular compound (polymer compound, polymer compound)
In embodiments of the present invention, can exist with gel state as the nonaqueous electrolyte of the mixture of nonaqueous solvents and electrolytic salt, wherein have the pbz polymer compound the maintenance thing (supporter, retainer).
The material of gelation can be used as macromolecular compound by lyosoption.Example comprises the copolymer of fluorine macromolecular compound such as polyvinylidene fluoride or vinylidene fluoride and hexafluoropropylene; Cross-linking products or the poly(ethylene oxide) of ether macromolecular compound as comprising poly(ethylene oxide); And the compound that comprises polyacrylonitrile, PPOX or polymethyl methacrylate as repetitive.Macromolecular compound can use separately or use as two or more mixtures.
From the angle of oxidation-reduction stability, preferred especially fluorine macromolecular compound wherein preferably contains the copolymer of vinylidene fluoride and hexafluoropropylene composition.In order to improve characteristic, this copolymer also can comprise the monoesters of unsaturated dibasic acid, as monomethyl maleate; Vinyl halides such as chloro trifluoro-ethylene (chlorotrifluoroethylene); The cyclic carbonate of unsaturated compound is as vinylene carbonate; Or contain acryloyl group vinyl (acrylvinyl) monomer of epoxy radicals.
The method that forms gel electrolyte layer hereinafter will be described.
Advantage
In first execution mode of the present invention, contain in the nonaqueous electrolyte by formula (I) and (II) at least a in the imide salt of expression, and at least a in heteropoly acid of representing by formula (III) to (VI) and the heteropoly compound.By this way, thereby the reaction that can suppress between electrode and the nonaqueous electrolytic solution reduces the gas generation, and therefore reduces the battery swelling of high temperature between the operating period.
2. second execution mode
Nonaqueous electrolyte battery according to second embodiment of the invention is below described.The nonaqueous electrolyte battery of second execution mode is cylindrical nonaqueous electrolyte battery.
(2-1) structure of nonaqueous electrolyte battery
Fig. 1 shows the profile construction of the nonaqueous electrolyte battery of second execution mode.Fig. 2 is the part zoomed-in view of the rolled electrode unit 20 shown in Fig. 1.This nonaqueous electrolyte battery is a kind of lithium rechargeable battery, wherein for example capacity of negative plates based on the embedding of electrode reaction material lithium with take off and imbed line display.
The unitary construction of nonaqueous electrolyte battery
This nonaqueous electrolyte battery is configured to mainly comprise cylindrical battery shell 11, rolled electrode unit 20 and a pair of insulation board 12 and 13 of hollow basically, and wherein rolled electrode unit 20 comprises the positive pole 21 and the negative pole 22 of reeling with the barrier film 23 of lamination therebetween.Rolled electrode unit 20 and insulation board 12 and 13 are contained in the cylindrical battery shell 11.Utilize the battery structure of such cylindrical battery shell 11 to make and be called cylindrical structural.
Battery case 11 is for example made by the iron (Fe) of nickel plating (Ni), and has a blind end and an openend.In the inside of battery container 11, this insulation board 12 and 13 is arranged on two sides of rolled electrode unit 20, perpendicular to coiling surface (pressed surface, rolled surface).
Via packing ring 17 joint fillings, battery case 11 usefulness are fixed to the battery cover 14 of openend of battery case 11 together with the relief valve mechanism 15 and the thermistor element (PTC that are arranged in the battery cover 14; Positive temperature coefficient) 16 seals.
Identical or the similar material that utilization is used for battery case 11 forms battery cover 14.Relief valve mechanism 15 is electrically connected to battery cover 14 via thermistor element 16, and when because the pressure of the inside battery that internal short-circuit or external heat cause when reaching certain level, cut off electrical connection between battery cover 14 and the rolled electrode unit 20 by the upset of discoid plate 15A.
Thermistor element 16 increases its resistance value at elevated temperatures, and the restriction electric current is to prevent the unusual heating owing to overcurrent.Packing ring 17 for example, is made of insulating material, and coating pitch is gone up on its surface.
Centrepin 24 is inserted into for example center of rolled electrode unit 20.The positive pole 21 of rolled electrode unit 20 is connected in for example positive wire 25 of aluminium (Al), and negative pole 22 is connected in for example negative wire 26 of nickel (Ni).Positive wire 25 is electrically connected to battery cover 14 by being soldered to relief valve mechanism 15.Negative wire 26 is electrically connected to battery case 11 by welding.
Anodal
The anodal 21 positive electrode active material layer 21B that are configured to comprise on the both sides that for example are arranged on plus plate current-collecting body 21A with a pair of surface.Positive electrode active material layer 21B also can only be arranged on the side of plus plate current-collecting body 21A.On anodal surface, form at least a coating come from by in formula (I) and the imide salt (II) represented.Notice that the deposit that forms on the positive pole forms according to the amount of adding the imide salt in the battery system to.
Plus plate current-collecting body 21A is by metal material, and for example aluminium, nickel and stainless steel constitute.
Positive electrode active material layer 21B comprises positive active material, and it is that one or more can embed the positive electrode with removal lithium embedded.As required, also can comprise other materials, as binding agent and conductive agent.
The preferred embodiment that can embed with the positive electrode of removal lithium embedded comprises lithium-containing compound, because it provides the ability of high-energy-density.The example of lithium-containing compound comprises the composite oxides that comprise lithium and transition metal; And the phosphate cpd that comprises lithium and transition metal.Among this,, preferably include the compound of at least a transition metal that is selected from cobalt, nickel, manganese and iron because it provides high-tension ability.
The example that comprises the composite oxides of lithium and transition metal comprises lithium cobalt composite oxide (Li xCoO 2), lithium nickel composite oxide (Li xNiO 2), lithium/nickel/cobalt composite oxide (Li xNi 1-zCo zO 2(z＜1)), lithium nickel cobalt manganese composite oxides (Li xNi (1-v-w)Co vMn wO 2(v+w＜1)) and the complex Li-Mn-oxide (LiMn of spinel structure 2O 4) or li-mn-ni compound oxide (LiMn 2-tNi tO 4(t＜2)).Among this, preferably contain the composite oxides of cobalt, because of they provide the ability of high power capacity and excellent cycle characteristics.The example that comprises the phosphate cpd of lithium and transition metal comprises LiFePO4 compound (LiFePO 4) and iron manganese phosphate lithium compound (LiFe 1-uMn uPO 4(u＜1)).
And, from providing even the higher chargeable property of electrode and the angle of cycle characteristics, can utilize composite particles, it makes by the surface that the fine particle with other lithium-containing compounds applies the core granule of any aforesaid lithium-containing compound.
Other examples that can embed with the positive electrode of removal lithium embedded comprise: oxide, as titanium oxide, vanadium oxide and manganese dioxide; Disulphide is as titanium disulfide and molybdenum bisuphide; Chalcogenide (chalcogenides) is as the selenizing niobium; Sulphur; And conducting polymer, as polyaniline and polythiophene.The positive electrode that can embed with removal lithium embedded can be different from these examples.And the mixture that can be used as two or more combination in any as the above positive electrode that exemplifies uses.
Negative pole
Negative pole 22 is configured to comprise, for example, is arranged on the negative electrode active material layer 22B on the both sides of the negative current collector 22A with a pair of surface.Negative electrode active material layer 22B can only be arranged on the side of negative current collector 22A.On negative terminal surface, form and come from by the heteropoly acid of formula (III) to (VI) expression and at least a coating of heteropoly compound.This coating comprises the deposit of the three-dimensional screen structure that forms by the heteropoly compound electrolysis in response to initial charge or charging.Coating is formed at least a portion of negative terminal surface, and comprises noncrystal polyacid and/or the polyacid compound that contains one or more multielements.Noncrystal polyacid and/or polyacid compound and nonaqueous electrolyte exist with gel state.
Be formed on the negative terminal surface and comprise the noncrystal polyacid of one or more polyacid elements and/or the gel coat of the embodiment of the present invention of polyacid compound can utilize SEM (scanning electron microscopy) to observe, for example, as shown in Figure 3.Notice that Fig. 3 is the SEM image of charging back negative terminal surface, dryly then obtaining after removing nonaqueous electrolyte by cleaning.
Can absorb the structural analysis that fine structure (XAFS) analysis is implemented based on X ray by the coating that on negative terminal surface, forms, and, confirm whether the deposit of noncrystal polyacid and/or polyacid compound exists according to the chemical information of the molecule that obtains by time of flight secondary ion massspectrometry method (ToF-SIMS).
Fig. 4 represents that wherein this nonaqueous electrolyte battery comprises the negative pole coating by the embodiment of the present invention that after adding silico-tungstic acid to battery system battery charge is formed by the example of the secondary ion spectrum of time of flight secondary ion massspectrometry method (ToF-SIMS) acquisition of the negative terminal surface of nonaqueous electrolyte battery.As from Fig. 4, seeing, there is the molecule that contains tungsten (W) and oxygen (O) conduct formation element.
Fig. 5 represents to absorb by the X ray from the negative terminal surface of nonaqueous electrolyte battery the example of the W-O key radial structure function that the Fourier transform of the spectrum that fine structure (XAFS) analyzes obtains, wherein this nonaqueous electrolyte battery comprise by adding silico-tungstic acid to battery system after to the charge negative pole coating of embodiment of the present invention of formation of battery.In conjunction with the analysis result of negative pole coating, Fig. 5 also represents the be used separately as polyacid of embodiment of the present invention and the wolframic acid (WO of heteropoly acid 3, WO 2) and silico-tungstic acid (H 4(SiW 12O 40) 26H 2The example of the radial structure function of W-O key O).
Can see that from Fig. 5 the sedimental peak L1 on the negative terminal surface appears at and silico-tungstic acid (H 4(SiW 12O 40) 26H 2O), tungsten dioxide (WO 2), tungstic acid (WO 3) peak L2, the L3 position different with L4, show that this deposit has different structures.Can confirm from radial structure function, at typical tungsten oxide tungstic acid (WO 3) and tungsten dioxide (WO 2) in, and at the initial substance silico-tungstic acid (H of embodiment of the present invention 4(SiW 12O 40) 26H 2O) in, main peak is 1.0 to 2.0
Figure BDA0000067554070000181
Scope exists, and other peaks are 2.0 to 4.0
Figure BDA0000067554070000182
Scope exists.
On the other hand, the W-O bond length that contains the main component wolframic acid in the embodiments of the present invention and be deposited on the polyacid on the both positive and negative polarity separates cloth, although the peak appears at this scope, and 1.0
Figure BDA0000067554070000191
To 2.0
Figure BDA0000067554070000192
Extraneous peak L1 does not relatively have different peaks.Particularly, 3.0
Figure BDA0000067554070000193
Below do not observe the peak basically.Therefore the deposit on this results verification negative terminal surface is noncrystal really.
For example copper, nickel and stainless steel constitute negative current collector 22A by metal material.
Negative electrode active material layer 22B comprises negative electrode active material, and it can be one or more negative materials that can embed with removal lithium embedded.As required, also can comprise other materials such as binding agent and conductive agent.The chargeable capacity that can embed with the negative material of removal lithium embedded is preferably greater than anodal discharge capacity.Notice that the details of binding agent and conductive agent is with described identical in conjunction with positive pole.
The negative material that can embed with removal lithium embedded can be, for example, and material with carbon element.The example of material with carbon element comprises and is easy to graphitisable carbon, has 0.37nm above (002) but the non-graphitized carbon of interplanar distance and the graphite with following (002) interplanar distance of 0.34nm.Instantiation comprises RESEARCH OF PYROCARBON, coke, vitreous carbon fiber, organic high molecular compound sintered product, activated carbon and carbon black.Coke comprises pitch coke, needle coke and petroleum coke.The organic high molecular compound sintered product is meant the carbonized product that obtains by sintering phenolic resins, furane resins etc. under suitable temperature.Material with carbon element is preferred, and is very little because they except being used as conductive agent, change on the crystal structure in embedding and removal lithium embedded, and high-energy-density and excellent cycle characteristics are provided thus.Material with carbon element can be fibrous, sphere-like, graininess or flakey in shape.
Except material with carbon element, the negative material that can embed with removal lithium embedded can be, for example, such material, its except can embed with removal lithium embedded, also comprise at least a in metallic element and the semimetallic elements as constituting element, because such material also provides high-energy-density.Such negative material can comprise independent or as the metallic element or the semimetallic elements of alloy or compound, or can comprise one or more phases of these materials at least in part.As used in this article, " alloy " contains the alloy of two or more metallic elements, and the alloy of one or more metallic elements and one or more semimetallic elements.And " alloy " can comprise nonmetalloid.Composition can be solid solution, eutectic (eutectic mixture) or interphase or the two or more mixture in these.
Metal and semimetallic elements are for example, can form those elements of alloy with lithium.Instantiation comprises magnesium (Mg), boron (B), aluminium (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), plumbous (Pb), bismuth (Bi), cadmium (Cd), silver (Ag), zinc (Zn), hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) and platinum (Pt).At least a in silicon and the tin is preferred, and silicon is preferred, because these element height can embed and removal lithium embedded, and can provide high-energy-density.
The example that comprises at least a negative material in silicon and the tin comprises silicon (simple substance, or as alloy or compound), tin (simple substance, or as alloy or compound), and the material that comprises these one or more phases at least in part.
The example of silicon alloy comprises those alloys that comprise at least a non-silicon second formation element that is selected from tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and the chromium (Cr).The example of the alloy of tin comprises those alloys that comprise at least a non-tin (Sn) the second formation element that is selected from silicon (Si), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb) and the chromium (Cr).
The example of tin compound and silicon compound comprises and containing, for example, and those compounds of oxygen (O) or carbon (C).Except tin (Sn) or silicon (Si), tin compound and silicon compound can comprise the above second formation element that exemplifies alternatively.
At least a negative material as comprising silicon (Si) and tin (Sn) particularly preferably is, and for example, comprises as the tin (Sn) of the first formation element and except first the second and the 3rd formation element that constitutes the element tin (Sn).Negative material can use together with the above negative material that exemplifies.Second to constitute element be to be selected from least a in cobalt (Co), iron (Fe), magnesium (Mg), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), silver (Ag), indium (In), cerium (Ce), hafnium (Hf), tantalum (Ta), tungsten (W), bismuth (Bi) and the silicon (Si).The 3rd to constitute element be to be selected from least a in boron (B), carbon (C), aluminium (Al) and the phosphorus (P).Comprise this second and element improved cycle characteristics.
The material that contains CoSnC is especially preferred, it comprises as the tin (Sn), cobalt (Co) and the carbon (C) that constitute element, and wherein carbon (C) content range is below the above 29.7 quality % of 9.9 quality %, and wherein the scope of the ratio (Co/ (Sn+Co)) of cobalt (Co) in tin (Sn) and cobalt (Co) total amount is more than the 30 quality % below the 70 quality %.Adopt these compositing ranges can obtain high-energy-density and excellent cycle characteristics.
As required, the material that contains SnCoC can comprise other alternatively and constitutes element.Other preferred embodiments that constitute element comprise silicon (Si), iron (Fe), nickel (Ni), chromium (Cr), indium (In), niobium (Nb), germanium (Ge), titanium (Ti), molybdenum (Mo), aluminium (Al), phosphorus (P), gallium (Ga) and bismuth (Bi), and the combination that they can be two or more is involved.Comprise that these elements further improve capacity characteristic or cycle characteristics.
The material that preferably contains SnCoC comprises stanniferous (Sn), cobalt (Co) and carbon (C) mutually, and this has low crystallization or non-crystal structure mutually.And, in containing the material of SnCoC, preferably constitute elemental carbon and be incorporated into other formation elements at least in part, that is, and metallic element or semimetallic elements.Carbon and combining of other elements have been suppressed the gathering or the crystallization of tin (Sn) or other elements, and this is considered to reduce cycle characteristics.
The state of element combination can pass through, and for example, x-ray photoelectron spectroscopy (XPS) is measured.In XPS, when the device that uses through calibration when providing the peak of gold atom 4f track (Au4f) at the 84.0eV place, for graphite, the peak of carbon 1s track (C1s) appears at the 284.5eV place.In surface contamination carbon, this peak appears at the 284.8eV place.On the contrary, when carbon charge density height, as in the carbon that for example is attached to metallic element or semimetallic elements the time, the peak of C1s occurs in being lower than the zone of 284.5eV.That is, when synthetic crest is being lower than when occurring in the zone of 284.5eV for the C1s that contains the SnCoC material, the carbon that comprises in containing the material of SnCoC (C) is incorporated into other at least in part and constitutes element, i.e. metallic element or semimetallic elements.
Notice that XPS utilizes, for example, the C1s peak carries out the spectral energy axis calibration.Usually, because the carbon of surface contamination is present on the surface, so the C1s peak of surface contamination carbon is set at 284.8eV, and as reference energy.In XPS, because the waveform at C1s peak as the waveform acquisition at peak that comprises surface contamination carbon and the peak that contains the carbon that comprises in the SnCoC material, for example is purchased the peak that software can separate the peak of surface contamination carbon and contain carbon contained in the SnCoC material so utilize.In waveform analysis, the position of the main peak on minimum binding energy side is as reference energy (284.8eV).
Other examples that can embed with the negative material of removal lithium embedded comprise the metal oxide and the macromolecular compound that can embed with removal lithium embedded.The example of such metal oxide comprises iron oxide, ruthenium-oxide and molybdenum oxide.The example of such macromolecular compound comprises polyacetylene, polyaniline and polypyrrole.
The negative material that can embed with removal lithium embedded can be different from these examples.And negative material such as above those mixtures that can be used as two or more combination in any that exemplify use.
Negative electrode active material layer 22B can utilize, for example, any means in vapor phase method, liquid phase method, spray-on process, sintering process and the cladding process, individually or two or more combinations form.When utilizing vapor phase method, liquid phase method, spray-on process or sintering process (individually or two or more combinations) when forming negative electrode active material layer 22B, preferably at least a portion place at the interface between negative electrode active material layer 22B and negative current collector 22A forms alloy.Particularly, the formation element of preferred negative current collector 22A is in being diffused into negative electrode active material layer 22B at the interface, and perhaps the formation element of negative electrode active material layer 22B is in being diffused into negative current collector 22A at the interface.And these constitute preferably phase counterdiffusion between negative current collector 22A and negative electrode active material layer 22B of element.By this way, can suppress because charging and the expansion of the negative electrode active material layer 22B that causes of discharge and the destruction that contraction causes, and can improve electron conduction between negative electrode active material layer 22B and the negative current collector 22A.
Vapor phase method can be, for example, and physical deposition method or chemical deposition, vacuum deposition method, sputtering method, ion plating method, laser ablation method, chemical vapor deposition (CVD) method or plasma chemical vapor deposition specifically.Known technology as electroplating and electroless coating, can be used as liquid phase method.Sintering process be a kind of wherein for example the particle negative electrode active material mix with other components such as binding agent, be dispersed in the solvent, and apply, be higher than the method for heat-treating under the temperature of binding agent fusing point for example then.Sintering process also can be utilized known technology implementation, for example, and as air calcination method, reaction sintering and hot pressing sintering method.
Barrier film
Barrier film 23 is set so that positive pole 21 and negative pole 22 are separated mutually, and allows the short circuit current of lithium ion by preventing from simultaneously to cause by the electrode contact.Barrier film 23 for example utilizes synthetic resin film such as polytetrafluoroethylene, polypropylene and poly perforated membrane or ceramic porous membrane structure.Barrier film 23 can be the plural layered product of these perforated membranes.The nonaqueous electrolytic solution dipping of above-mentioned first execution mode of barrier film 23 usefulness.
(2-2) manufacture method of nonaqueous electrolyte battery
Nonaqueous electrolyte battery can be made as follows.
Anodal manufacturing
Begin to make with anodal 21.For example, positive electrode, binding agent and conductive agent are mixed to obtain cathode mix, then it is dispersed in the organic solvent, and form pasty state cathode mix slurry.For example utilize scraper or scraping strip coating machine that the cathode mix slurry evenly is coated on two surfaces of plus plate current-collecting body 21A then.After the drying, for example under optional heating, utilize roll squeezer, and form positive electrode active material layer 21B the coating press forming.Press forming can repeat repeatedly.
The manufacturing of negative pole
Next make negative pole 22.For example, negative material, binding agent and optional conductive agent are mixed and acquisition negative pole mixture, then it is dispersed in the organic solvent, and forms pasty state cathode mix slurry.For example utilize scraper or scraping strip coating machine that the cathode mix slurry evenly is coated on two surfaces of plus plate current-collecting body 22A then.After the drying, for example under optional heating, utilize roll squeezer, and form negative electrode active material layer 22B the coating press forming.
The assembling of nonaqueous electrolyte battery
Positive wire 25 and negative wire 26 are connected to plus plate current-collecting body 21A and negative current collector 22A respectively by for example welding.Then positive pole 21 and negative pole 22 are reeled via barrier film 23, and positive wire 25 and negative wire 26 are respectively welded to relief valve mechanism 15 and battery case 11 at front end.Coiling body with positive pole 21 and negative pole 22 is clipped between insulation board 12 and 13 then, and is contained in battery case 11 inside.Under the situation of positive pole 21 that is contained in battery case 11 inside and negative pole 22, the nonaqueous electrolytic solution of first execution mode is injected in the battery case 11, and with this electrolyte dipping of barrier film 23 usefulness.Then, battery cover 14, relief valve mechanism 15 and thermistor element 16 are fixed to the openend of battery case 11 via packing ring 17 joint fillings.As a result of, obtained the nonaqueous electrolyte battery shown in Fig. 2 and Fig. 3.
In the nonaqueous electrolyte battery of as above constructing, the anion of formula that contains in the nonaqueous electrolytic solution (I) or imide salt (II) is adsorbed on anodal surface when initial charge.As a result of, suppressed the reaction between electrode and the nonaqueous electrolytic solution, and reduced particularly in the gas generation of high temperature between the operating period.
And formula (III) also deposits to the heteropoly acid and at least a generation electrolysis in the heteropoly compound of (VI), thereby forms coating on negative terminal surface.Any one heteropoly compound of formula (III) to (VI) can embed and the removal lithium embedded ion, and therefore by being comprised in the nonaqueous electrolytic solution, in response to charging and the discharge in initial the use, this heteropoly compound forms the stable SEI coating on negative pole, and suppresses the decomposition of solvent and electrolytic salt in the nonaqueous electrolytic solution.The SEI that is formed by heteropoly acid and/or heteropoly compound is inorganic and firm, and to the embedding of lithium ion with take off embedding and have small resistor.Therefore think, this SEI can not cause such as capacity deterioration adverse effect.And, think to be similar to the lithium salts in the nonaqueous electrolyte for Monofluorophosphate and/or the difluorophosphoric acid salt that adds with heteropoly acid and/or heteropoly compound, further suppress the decomposition of electrolytic salt, and form low resistance SEI.
Therefore the nonaqueous electrolytic solution of embodiment of the present invention soaks into negative electrode active material layer 22B, and comes from the heteropoly acid of formula (III) to (VI) and at least a compound in the heteropoly compound and can be deposited among the negative electrode active material layer 22B in response to charging or initial charge.Particularly, coming from the heteropoly acid of formula (III) to (VI) and at least a compound in the heteropoly compound may reside between the anode active material particles.
Similarly, because nonaqueous electrolytic solution soaks into positive electrode active material layer 21B, so heteropoly acid of the formula of coming from (III) to (VI) and at least a compound in the heteropoly compound can be in response to charging or initial charge and be deposited among the positive electrode active material layer 21B.In other words, coming from the heteropoly acid of formula (III) to (VI) and at least a compound in the heteropoly compound may reside between the positive active material particle.
Come from the heteropoly acid of formula (III) to (VI) and at least a compound in the heteropoly compound and in the negative pole coating, whether exist, can confirm by for example x-ray photoelectron power spectrum (XPS) analysis or time of flight secondary ion massspectrometry method (ToF-SIMS).In this case, after the dismounting battery, wash battery with dimethyl carbonate.Battery is gone up low voc solvent component and the electrolytic salt that exists through flushing thereby remove the surface.Preferably, sampling is carried out under the atmosphere of inertia as far as possible.
Advantage
In second execution mode of the present invention, utilize nonaqueous electrolyte battery, it is included at least a in the heteropoly acid of at least a and formula (III) to (VI) of formula (I) in the nonaqueous electrolyte and imide salt (II) and the heteropoly compound.By this way, can be suppressed at the deterioration of the battery behavior under the hot environment, and in the side reaction that can suppress electrode active material and nonaqueous electrolytic solution continuously between the operating period.As a result of, improved battery behavior.Because interpolation imide salt and heteropoly compound are also effective for the use under the hot environment among the present invention, so the present invention can be applicable to primary cell and secondary cell.Preferably, the present invention is used for secondary cell, because the present invention is more effective in having the battery of a plurality of charge and discharge cycles.
3. the 3rd execution mode
Nonaqueous electrolyte battery according to the 3rd execution mode of the present invention is described below.The nonaqueous electrolyte battery of the 3rd execution mode is the lamination membranous type nonaqueous electrolyte battery with laminated film outside (packing).
(3-1) structure of nonaqueous electrolyte battery
Nonaqueous electrolyte battery according to third embodiment of the invention has been described.Fig. 6 is the decomposition diagram of expression according to the structure of the nonaqueous electrolyte battery of third embodiment of the invention.Fig. 7 is the amplification view at the 30 online I-I places, rolled electrode unit of Fig. 6.
This nonaqueous electrolyte battery is configured to comprise membranaceous external member 40 basically and is contained in rolled electrode unit 30 in the external member 40, and wherein positive wire 31 and negative wire 32 are connected to this rolled electrode unit 30.Utilize the battery structure of membranaceous external member 40 to be called the laminated film structure.
For example, positive wire 31 is drawn from external member 40 with identical direction with negative wire 32.Positive wire 31 for example utilizes metal material such as aluminium to form.Negative wire 32 utilizes for example metal material such as copper, nickel and stainless steel formation.These metal materials for example form thin plate or screen cloth.
External member 40 utilizes for example aluminium lamination press mold formation, and this aluminium lamination press mold comprises nylon membrane, aluminium foil and the polyethylene film of lamination in the following order.For example, external member 40 is by constituting in the welding of periphery place or with the bonding a pair of rectangular aluminum laminated film of adhesive, and wherein polyethylene film is towards rolled electrode unit 30.
The adhesive film 41 that stops extraneous air to enter is inserted between external member 40 and positive and negative lead wires 31 and 32.Adhesive film 41 utilizes has adhering material structure to positive wire 31 and negative wire 32.The example of such material comprises vistanex such as polyethylene, polypropylene, modified poly ethylene and modified polypropene.
External member 40 can replace the aluminium lamination press mold by the laminated film of other laminar structures, or by polypropylene or other polymer films, or metal film constitutes.
Fig. 7 is the cutaway view of the rolled electrode unit 30 I-I interceptings along the line of Fig. 6.Rolled electrode unit 30 is via the positive pole 33 of barrier film 35 and electrolyte 36 laminations and the winder unit of negative pole 34.The outermost peripheral of rolled electrode unit 30 is by boundary belt 37 protections.
Anodal 33 are configured to comprise for example positive electrode active material layer 33B on plus plate current-collecting body 33A both sides, and form at least a coating in the imide salt that comes from formula (I) and formula (II) on anodal surface.
Negative pole 34 is configured to comprise for example negative electrode active material layer 34B on the both sides of negative current collector 34A, and formation comes from formula (III) to the heteropoly acid of (VI) and at least a coating in the heteropoly compound on negative terminal surface.The heteropoly compound coating is the deposit by the tridimensional network of heteropoly compound electrolysis formation, and the nonaqueous electrolytic solution in this structure exists as the gel coat that contains noncrystal polyacid in battery system.
Anodal 33 and negative pole 34 so that negative electrode active material layer 34B and the mode of positive electrode active material layer 33B on opposition side be provided with.Plus plate current-collecting body 33A, positive electrode active material layer 33B, negative current collector 34A, negative electrode active material layer 34B and barrier film 35 respectively with the same way as structure of plus plate current-collecting body 21A, positive electrode active material layer 21B, negative current collector 22A, negative electrode active material layer 22B and the barrier film 23 of second execution mode.
Electrolyte 36 is so-called gel electrolytes, comprises the nonaqueous electrolytic solution of first execution mode and keeps the macromolecular compound of this nonaqueous electrolytic solution.Gel electrolyte is preferred, because it provides high ionic conductance (for example, being more than the 1mS/cm under the room temperature), and prevents to leak.
(3-2) manufacture method of nonaqueous electrolyte battery
For example, utilize following three kinds of manufacture methods (first to the 3rd manufacture method) to make nonaqueous electrolyte battery.
(3-2-1) first manufacture method
In first manufacture method, for example, the program according to being used to form positive pole 21 and negative pole 22 in second execution mode at first is formed on positive electrode active material layer 33B on the both sides of plus plate current-collecting body 33A, thereby forms anodal 33.Negative electrode active material layer 34B is formed on the both sides of negative current collector 34A, thereby forms negative pole 34.
With the precursor solution of the nonaqueous electrolytic solution that contains first execution mode, macromolecular compound and solvent of preparation separately be coated in anodal 33 and negative pole 34 on, and evaporating solvent is to form gel electrolyte 36.Then, positive wire 31 and negative wire 32 are connected respectively to plus plate current-collecting body 33A and negative current collector 34A.
The positive pole 33 and the negative pole 34 that will have electrolyte 36 then carry out lamination via barrier film 35, and reel in a longitudinal direction.Then boundary belt 37 is bonded to most peripheral, thereby makes rolled electrode unit 30.At last, rolled electrode unit 30 is placed between for example a pair of membranaceous external member 40, and seal within it at periphery place bonding external member 40 by for example hot melt.Adhesive film 41 is inserted between positive wire 31 and negative wire 32 and the external member 40.This has finished nonaqueous electrolyte battery.
(3-2-2) second manufacture method
In second manufacture method, at first, positive wire 31 and negative wire 32 are connected respectively to positive pole 33 and negative pole 34.Then with anodal 33 and negative pole 34 carry out lamination with therebetween barrier film 35 and reel, and boundary belt 37 is bonded to outermost peripheral, thereby obtains winder unit as the precursor of rolled electrode unit 30.
Then, winder unit is placed between a pair of membranaceous external member 40, subsequently it is kept a side opening by for example hot melt in periphery place bonding.As a result of, this winder unit is contained in the bag of external member 40.Then, the preparation electrolyte composition, it comprises the nonaqueous electrolytic solution of first execution mode, starting monomer, polymerization initiator and the optional material such as the polymerization inhibitor of macromolecular compound, and this electrolyte composition is injected the bag of external member 40.By the opening sealing of hot melt for example with external member 40.At last, with monomer hot polymerization synthetic macromolecular compound, and form gel electrolyte 36.This has finished nonaqueous electrolyte battery.
(3-2-3) the 3rd manufacture method
In the 3rd manufacture method, except macromolecular compound being coated in advance on barrier film 35 both sides, according to mode identical in second manufacture method form winder unit and with its be contained in external member 40 the bag in.
The macromolecular compound that is coated on the barrier film 35 can for example be the polymer that comprises the vinylidene fluoride component, homopolymers, copolymer or multicomponent copolymer specifically.The terpolymer that instantiation comprises polyvinylidene fluoride, comprises the bipolymer of vinylidene fluoride and hexafluoropropylene component and comprise vinylidene fluoride, hexafluoropropylene and chloro trifluoro-ethylene component.
Notice that except the polymer that comprises the vinylidene fluoride component, this macromolecular compound can also comprise one or more other macromolecular compounds.Then, prepare the nonaqueous electrolytic solution of first execution mode, and inject external member 40, and by for example hot melt the opening of sealed external member 40.At last, external member 40 heats under applied load, thereby via macromolecular compound barrier film 35 is contacted with negative pole 34 with anodal 33.As a result of, nonaqueous electrolytic solution soaks into macromolecular compound, causes the macromolecular compound gelation and forms electrolyte 36.This has finished nonaqueous electrolyte battery.
Initial charge or charging by the nonaqueous electrolyte battery that makes according to first to the 3rd manufacture method, the anion of formula (I) or imide salt (II) is adsorbed on electrode surface, and comes from formula (III) to the heteropoly acid of (VI) and at least a coating in the heteropoly compound in negative terminal surface formation.
Advantage
The effect that obtains in second execution mode also can obtain in the 3rd execution mode.
4. the 4th execution mode
Nonaqueous electrolyte battery according to four embodiment of the invention is described below.The nonaqueous electrolyte battery of the 4th execution mode is the lamination membranous type nonaqueous electrolyte battery with laminated film outer packaging, and does not have differently with the nonaqueous electrolyte battery of the 3rd execution mode, just directly utilizes the nonaqueous electrolytic solution of first execution mode.Therefore, following description relates generally to different with the 3rd execution mode.
(4-1) structure of nonaqueous electrolyte battery
Nonaqueous electrolyte battery according to four embodiment of the invention utilizes nonaqueous electrolytic solution rather than gel electrolyte 36.Therefore, rolled electrode unit 30 does not comprise electrolyte 36, but comprises the nonaqueous electrolytic solution that soaks into barrier film 35.
(4-2) manufacture method of nonaqueous electrolyte battery
Nonaqueous electrolyte battery can for example be made as follows.
At first, for example, positive active material, binding agent and conductive agent are mixed, thereby the preparation cathode mix is dispersed in it in solvent such as the N-N-methyl-2-2-pyrrolidone N-subsequently, thereby obtains the cathode mix slurry.With the cathode mix slurry be coated on the both sides, dry and press forming, thereby form positive electrode active material layer 33B, and obtain anodal 33.Afterwards, positive wire 31 for example is connected to plus plate current-collecting body 33A by ultra-sonic welded or spot welding.
For example, negative material and binding agent are mixed, thereby preparation negative pole mixture is dispersed in it in solvent such as the N-N-methyl-2-2-pyrrolidone N-subsequently, thereby obtains the negative pole mixture paste.The negative pole mixture paste is coated on the both sides of negative current collector 34A, dry and press forming, thereby form negative electrode active material layer 34B, and obtain anodal 34.Afterwards, negative wire 32 for example is connected to negative current collector 34A by ultra-sonic welded or spot welding.
Positive pole 33 and negative pole 34 are reeled with barrier film 35 therebetween, and are installed in the external member 40.Then, with the nonaqueous electrolytic solution injection external member 40 of first execution mode, and sealed external member 40.As a result of, obtained the nonaqueous electrolyte battery shown in Fig. 6 and 7.
Advantage
The effect that obtains in second execution mode also can obtain in the 4th execution mode.
5. the 5th execution mode
Representative configuration according to the nonaqueous electrolyte battery 20 of fifth embodiment of the invention is described below.Nonaqueous electrolyte battery 20 according to fifth embodiment of the invention has rectangular shape, as shown in Figure 8.
Nonaqueous electrolyte battery 20 is made as follows.As shown in Figure 8, at first rolled electrode unit 53 is contained in the shell 51, shell 51 is by the metal metal rectangular shell made of aluminium (Al) and iron (Fe) for example.
Then, the electrode pin 54 that is arranged on the battery cover 52 is connected to the electrode terminal 55 of drawing from rolled electrode unit 53, and utilizes battery cover 52 to seal.Then, by nonaqueous electrolytic solution inlet 56, to comprise formula (I) or imide salt (II) and the heteropoly acid of formula (III) to (VI) and at least a nonaqueous electrolytic solution in the heteropoly compound and be injected into nonaqueous electrolyte battery, then it be sealed with containment member 57.Charging or initial charge in response to the battery of making like this, the anion of formula (I) or imide salt (II) is adsorbed on the electrode surface, and comes from the heteropoly acid of formula (III) to (VI) expression and at least a compound in the heteropoly compound is deposited on the surface of negative pole 14.This has finished the nonaqueous electrolyte battery 20 of fifth embodiment of the invention.
Notice that rolled electrode unit 53 passes through via the membrane layer positive pressure utmost point and negative pole, and rolled electrode obtains.That describes in positive pole, negative pole, barrier film and nonaqueous electrolytic solution and first execution mode is identical, and is not described further.
Advantage
The gas that the nonaqueous electrolyte battery 20 of fifth embodiment of the invention can suppress under capability retention reduction and the hot environment produces, and the reduction of capability retention between the operating period continuously.Therefore, can prevent because gas produces damage and the battery behavior reduction that internal pressure causes of increasing that causes.
6. the 6th execution mode
Nonaqueous electrolyte battery according to sixth embodiment of the invention is described below.Nonaqueous electrolyte battery according to the 6th execution mode is a lamination membranous type nonaqueous electrolyte battery, wherein as the electrode unit of the layered product of anodal and negative pole with the laminated film covering (shroud, sheath).Except the structure of electrode unit, the 6th execution mode does not have different with the 3rd execution mode.Therefore, following description only relates to the electrode unit of the 6th execution mode.
Positive pole and negative pole
As shown in Figure 9, by on the both sides of rectangle plus plate current-collecting body, forming positive electrode active material layer, and obtain anodal 61.Preferably, anodal 61 plus plate current-collecting body and positive terminal are whole forms.Similarly, by on the rectangle negative current collector, forming negative electrode active material layer, and obtain negative pole 62.
Anodal 61 and negative pole 62 with therebetween barrier film 63 lamination successively, and form electrode layered product 60.Can wait the laminated state that keeps the electrode in the electrode layered product 60 by adhering to insulating tape.Electrode layered product 60 for example covers with laminated film, and in nonaqueous electrolytic solution is sealed in battery.Can utilize gel electrolyte to replace nonaqueous electrolytic solution.
Embodiment
Specific embodiments of the invention are described below.Yet, should be noted that the present invention is not limited by following description.
Following imide salt is used for embodiment and Comparative Examples.
Compd A: two (fluorine sulphonyl) imines lithium
Compd B: two (fluoroform sulphonyl) imines lithium
Compound C: two (five fluorine second sulphonyl) imines lithium
Compound D: two (nine fluorine fourth sulphonyl) imines lithium
Compd E: perfluoropropane-1,3-disulfonyl imines lithium
Figure BDA0000067554070000311
Following heteropoly acid is used for embodiment and Comparative Examples.Notice that following heteropoly acid all comprises the polyacid ion of Keggin structure.
Compound F 17-hydroxy-corticosterone: silicomolybdic acid heptahydrate
Compound G: silico-tungstic acid heptahydrate
Compound H: phosphomolybdic acid heptahydrate
Compound I: phosphotungstic acid heptahydrate
Notice that the quality of heteropoly acid is not comprise the quality of heteropoly acid in conjunction with the quality of water.Similarly, the quality of heteropoly compound is not comprise the quality of heteropoly compound in conjunction with the quality of water.
Embodiment 1
Among the embodiment 1, add the characteristic of estimating the lamination membrane-type cell under the amount of the imide salt of electrolyte and heteropoly acid in variation.
Embodiment 1-1
Anodal manufacturing
Positive electrode active material lithium cobalt/cobalt oxide (LiCoO with 94 mass parts 2), the binding agent polyvinylidene fluoride (PVdF) of the conductive agent graphite of 3 mass parts and 3 mass parts mixes, and adds the N-methyl pyrrolidone, thereby obtain anodal mixed slurry.Should be coated in equably on the thick aluminium foil two sides of 10 μ m by the positive pole mixed slurry then, drying, and use roll squeezer compression moulding, thus obtain to be provided with the positive plate of positive electrode active material layer (bulk density is 3.40g/cc).At last, it is that 50mm and length are 300mm that positive plate is cut into width, and aluminium (Al) positive wire is welded to an end of this plus plate current-collecting body, thereby obtains anodal.
The manufacturing of negative pole
With the negative electrode active material mesoporous carbon microballon (mesocarbon microbead) of 97 mass parts (MCMB) and the binding agent polyvinylidene fluoride (PVdF) of 3 mass parts mix, and add the N-methyl pyrrolidone, thereby obtain the negative pole mixed slurry.Then the negative pole mixed slurry is coated in equably on the two sides of the thick Copper Foil (negative current collector) of 10 μ m, drying, and use roll squeezer compression moulding, thus the negative plate that acquisition has negative electrode active material layer (bulk density is 1.80g/cc).At last, negative plate is cut into width 50mm and length 300mm, and nickel (Ni) negative wire is welded to an end of negative current collector, thereby obtain negative pole.
The adjustment of nonaqueous electrolytic solution
Electrolytic salt lithium hexafluoro phosphate (LiPF with 0.99mol/kg 6) and two (fluorine sulphonyl) imines lithiums (imide salt, compd A) of 0.01mol/kg totally being in the mixture of the amount of 0.1mol/kg 3: 7 (mass ratio) adding ethylene carbonate (EC) and diethyl carbonate (DEC) to.Then, the silicomolybdic acid heptahydrate of 0.5 weight % (heteropoly acid, compound F 17-hydroxy-corticosterone) is dissolved in wherein.
The battery assembling
Anodal and negative pole are carried out lamination via the barrier film that provides with the thick capillary polypropylene form membrane of 7 μ m.This layered product is reeled repeatedly along the longitudinal direction of this layered product, and terminal part is fixed with adhesive tape, thereby obtain flattened roll around electrode unit.Then, this rolled electrode unit is placed the bag shape external member of aluminium lamination press mold.After injecting 2g electrolyte, this sack of hot melt under decompression power, thereby the opening of sealed aluminum laminated film.The lamination membrane-type cell of embodiment 1-1 makes by this way.
After initial charge, confirmed on negative terminal surface, to form gel coat in the battery of dismounting.
Embodiment 1-2
Except adding the imide salt compd A of 0.025mol/kg, be outside the 1.0mol/kg thereby make the total amount of electrolytic salt, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Embodiment 1-3
Except adding the imide salt compd A of 0.05mol/kg, be outside the 1.0mol/kg thereby make the total amount of electrolytic salt, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Embodiment 1-4
Mix the heteropoly compound F except amount, make the lamination membrane-type cell in the mode identical with embodiment 1-1 with 0.01 weight %.
Embodiment 1-5
Mix the heteropoly compound F except amount, make the lamination membrane-type cell in the mode identical with embodiment 1-1 with 0.05 weight %.
Embodiment 1-6
Mix the heteropoly compound F except amount, make the lamination membrane-type cell in the mode identical with embodiment 1-1 with 0.1 weight %.
Embodiment 1-7
Mix the heteropoly compound F except amount, make the lamination membrane-type cell in the mode identical with embodiment 1-1 with 0.5 weight %.
Embodiment 1-8
Mix the heteropoly compound F except amount, make the lamination membrane-type cell in the mode identical with embodiment 1-1 with 1.0 weight %.
Embodiment 1-9
Mix the heteropoly compound F except amount, make the lamination membrane-type cell in the mode identical with embodiment 1-1 with 2.0 weight %.
Embodiment 1-10
Except thereby the imide salt compd A that adds 0.2mol/kg makes the total amount of electrolytic salt is 1.0mol/kg, makes the lamination membrane-type cell in the mode identical with embodiment 1-1.
Embodiment 1-11
Except adding the imide salt compd A of 0.3mol/kg, be 1.0mol/kg thereby make the total amount of electrolytic salt, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Embodiment 1-12 to 1-22
Except the composition of electrolytic solution, it contains outside the vinylene carbonate (VC) as the nonaqueous solvents interpolation of 1.0 weight %, makes the lamination membrane-type cell in the mode identical with embodiment 1-1 to 1-11.
Comparative example 1-1
Except the vinylene carbonate (VC) that adds 1.0 weight % as the nonaqueous electrolyte solvent, and do not add outside imide salt compd A and the heteropoly compound F, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-2
Except the vinylene carbonate (VC) that adds 1.0 weight % as the nonaqueous electrolyte solvent, and the concentration with 0.1mol/kg is added the imide salt compd A, do not add outside the heteropoly compound F simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-3
Except the vinylene carbonate (VC) that adds 1.0 weight % as the nonaqueous electrolyte solvent, and the concentration with 0.2mol/kg is added the imide salt compd A, do not add outside the heteropoly compound F simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-4
Except the vinylene carbonate (VC) that adds 1.0 weight % as the nonaqueous electrolyte solvent, and mix the heteropoly compound F of 0.5 weight %, do not mix outside the imide salt compd A simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-5
Except the vinylene carbonate (VC) that adds 1.0 weight % as the nonaqueous electrolyte solvent, and mix the heteropoly compound F of 1.0 weight %, do not mix outside the imide salt compd A simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-6
Except the vinylene carbonate (VC) that adds 5.0 weight % as the nonaqueous electrolyte solvent, and do not add outside imide salt compd A and the heteropoly compound F, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-7
Except the vinylene carbonate (VC) that adds 5.0 weight % as the nonaqueous electrolyte solvent, and the concentration with 0.1mol/kg is added the imide salt compd A, do not add outside the heteropoly compound F simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-8
Except the vinylene carbonate (VC) that adds 5.0 weight % as the nonaqueous electrolyte solvent, and the concentration with 0.2mol/kg is added the imide salt compd A, do not add outside the heteropoly compound F simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-9
Except the carbonic acid fluorine second diester (FEC) that adds 1.0 weight % as the nonaqueous electrolyte solvent, and do not add outside imide salt compd A and the heteropoly compound F, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-10
Except the carbonic acid fluorine second diester (FEC) that adds 1.0 weight % as the nonaqueous electrolyte solvent, and the concentration with 0.1mol/kg is added the imide salt compd A, do not add outside the heteropoly compound F simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-11
Except the carbonic acid fluorine second diester (FEC) that adds 1.0 weight % as the nonaqueous electrolyte solvent, and the concentration with 0.2mol/kg is added the imide salt compd A, do not add outside the heteropoly compound F simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-12
Except the carbonic acid fluorine second diester (FEC) that adds 5.0 weight % as the nonaqueous electrolyte solvent, and do not add imide salt compd A and heteropoly compound F, with the mode making layer press mold type battery identical with embodiment 1-1.
Comparative example 1-13
Except the carbonic acid fluorine second diester (FEC) that adds 5.0 weight % as the nonaqueous electrolyte solvent, and the concentration with 0.1mol/kg is added the imide salt compd A, do not add outside the heteropoly compound F simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
Comparative example 1-14
Except the carbonic acid fluorine second diester (FEC) that adds 5.0 weight % as the nonaqueous electrolyte solvent, and the concentration with 0.2mol/kg is added the imide salt compd A, do not add outside the heteropoly compound F simultaneously, make the lamination membrane-type cell in the mode identical with embodiment 1-1.
The cell evaluation of embodiment and comparative example is as follows.
Cell evaluation
(a) degree of battery swelling after the initial charge
After the initial cells thickness of the battery of measuring each embodiment and comparative example, in 23 ℃ of environment under the 800mA constant current with battery charge to 4.2V voltage, and under constant voltage 4.2V further charging to reach total charging time be 3 hours.Measure the cell thickness after the initial charge then.In order to find the degree of battery swelling, according to the variation of cell thickness after the following equation calculating initial charge.
The variation of cell thickness (%) after the initial charge=(cell thickness after the initial charge/initial cells thickness) * 100
(b) high temperature circulation test
In 23 ℃ of environment, under constant current 0.5C, supreme the rationing the power supply of each battery charge pressed 4.2V, and further to charge to charging current under constant voltage 4.2V be 0.05C.Then under 0.5C with battery discharge to whole voltage 3.0V.This charging and discharge cycles repeat twice, and measure the discharge capacity after the circulation for the second time.
Then, this charging and discharge cycles repeat 300 circulations subject to the foregoing in 50 ℃ of environment, and measure the discharge capacity after the circulation 300 times.Calculate the discharge capacitance that circulates the back for 300 times with respect to the discharge capacity after circulating for the second time according to following equation.
Discharge capacitance (%)=(discharge capacity after time circulation of discharge capacity/2 after 300 circulations) * 100
Notice that " 0.5C " is the current value that theoretical capacity discharged fully in 2 hours.
(c) high temperature trickle charge test
Measure the thickness of preceding each battery of charging.Battery charges to the 4.25V upper voltage limit under the 0.5C constant current in 50 ℃ of environment, and further charge to the current value of 0.05C under the 4.25V constant voltage.Continuing charging 300 hours to whole electric current in equivalent environment is 0mA, and measures the cell thickness after the trickle charge.
Increase according to cell thickness after the following equation calculating high temperature trickle charge.
Cell thickness increases (%)=(cell thickness before the cell thickness increase/charging after the trickle charge) * 100
(d) discharge capacitance after the high temperature trickle charge
The battery of trickle charge under 0.5C the discharge capacitance of constant-current discharge to the whole voltage 3.0V as definite during the trickle charge of (c) high temperature is tested.Discharge capacitance after the high temperature trickle charge calculates according to following equation.
Discharge capacitance after the high temperature trickle charge (%)=(discharge capacity after time circulation of the discharge capacity of high temperature trickle charge/2) * 100
(e) variation of the amount of detected metallic atom on the electrode surface
Dismounting is in the battery of the discharge condition after initial charge and discharge back and the high temperature trickle charge.Then, the negative terminal surface of observing the battery of each dismounting with SEM-EDX, and measure the amount of the metallic atom that comes from the heteropoly acid on the negative terminal surface.Calculate the variation of the amount of the metallic atom in the battery after the high temperature trickle charge then.
" metallic atom " measured among the embodiment 1 is the molybdenum atom in the silicomolybdic acid heptahydrate (heteropoly acid, compound F 17-hydroxy-corticosterone) that adds in the electrolyte.More little variation means few more dissolving, and therefore stable more in the initial SEI coating that forms of negative terminal surface, and therefore shows in high temperature few more deterioration between the operating period.
Note, only the embodiment 1-1 to 1-22 that adds heteropoly acid and Comparative Examples 1-4 and 1-5 are measured.
Following table 1 and 2 shows result of the test.
Table 1
Figure BDA0000067554070000391
Table 1 (continuing)
Figure BDA0000067554070000401
Table 2
Figure BDA0000067554070000402
Table 2 (continuing)
As can be seen, utilize the nonaqueous electrolyte that comprises according to imide salt of the present invention and heteropoly acid to improve the battery behavior under the hot environment from the result shown in table 1 and 2.
For example, compare with the comparative example 1-1 that does not wherein add imide salt and heteropoly acid, the capability retention that has wherein added among the embodiment 1-15 to 1-20 of imide salt and heteropoly acid is significantly improved.Can also see that the variation of cell thickness is less.
And, by comparing embodiment 1-15 to 1-20 and comparative example 1-2, as can be seen, added all therein that battery behavior improves among the embodiment 1-15 to 1-20 of imide salt (0.1mol/kg) and heteropoly acid.
As finding out that with the comparison of comparative example 1-2 and 1-3 (only adding imide salt) interpolation of imide salt improves battery behavior to a certain extent from comparative example 1-1 (not adding imide salt and heteropoly acid).This improvement is considered to because imide salt suppresses anodal deterioration.Find to utilize the nonaqueous electrolyte that only contains imide salt to improve the resistance of trickle charge.Yet with regard to the cell thickness increase that suppresses to be caused by the gas generation, such nonaqueous electrolyte is inadequate.
Also find from comparative example 1-4 and 1-5, only add the deterioration that heteropoly acid can not improve discharge capacity under the high temperature.This thinks because insufficient high-temperature stability of the heteropoly acid SEI coating that forms in initial charge, because it is dissolved and can not show effect to lack imide salt.Therefore, increase of the cell thickness after the high temperature trickle charge and discharge capacity can utilize the nonaqueous electrolyte that contains with good grounds imide salt of the present invention and heteropoly acid to improve.
By comparing comparative example and embodiment, imide salt is added in discovery simultaneously and heteropoly acid significantly improves battery behavior, comprises high discharge capacitance and baby battery varied in thickness, and no matter the amount of adding.
Unless add imide salt and heteropoly acid, otherwise utilize carbonic acid fluorine second diester (FEC) not improve battery behavior as cyclic carbonate.In the presence of imide salt, increase the amount of reactive cyclic carbonate vinylene carbonate (VC) and carbonic acid fluorine second diester (FEC), do not improve the battery behavior of high temperature between the operating period, make the battery behavior variation on the contrary.Be known that cyclic carbonate decomposes and formation negative pole coating, it suppresses the reaction with electrolyte.Yet, find can not fully suppress the decomposition reaction of imide salt, and aforementioned effect is provided by the inorganic coating that comes from heteropoly acid to a great extent at negative pole from organic negative pole coating that the mixture of cyclic carbonate and imide salt obtains.
Find that from embodiment the heteropoly acid of the imide salt of 0.01mol/kg and at least 0.01 weight % exists jointly at least, during effectively suppressing trickle charge in the side reaction at positive pole and negative pole place and to improve aspect the hot properties be very effective.Also find the decline of the discharge capacity that the existence inhibition of heteropoly acid is relevant with the amount of the imide salt that increases.
The common existence of also finding imide salt and heteropoly acid is highly effective, even under the situation of the cyclic carbonate that is not used as nonaqueous solvents.Utilization contains the nonaqueous electrolyte of cyclic carbonate, even further improves effect.
Embodiment 2
Among the embodiment 2, estimate the characteristic of lamination membrane-type cell to the various combination of E and heteropoly compound F to I with the imide salt compd A.
Embodiment 2-1
Except in nonaqueous solvents, mixing the vinylene carbonate (VC) of 1.0 weight %, and use two (fluorine sulphonyl) imines lithium (imide salts of 0.01mol/kg, compd A), silicomolybdic acid heptahydrate (heteropoly acid with 0.5 weight %, compound F 17-hydroxy-corticosterone) outside, with embodiment 1-1 in identical mode make the lamination membrane-type cell.
Embodiment 2-2 to 2-4
Except using silico-tungstic acid heptahydrate (compound G), phosphomolybdic acid heptahydrate (compound H) and phosphotungstic acid heptahydrate (Compound I) as the heteropoly acid, with embodiment 2-1 in identical mode make the lamination membrane-type cell.
Embodiment 2-5 to 2-8
Except using two (fluoroform sulphonyl) the imines lithiums (compd B) of imide salt, with embodiment 2-1 to 2-4 in identical mode make the lamination membrane-type cell.
Embodiment 2-9 to 2-12
Except using two (five fluorine second sulphonyl) the imines lithiums (Compound C) of imide salt, with embodiment 2-1 to 2-4 in identical mode make the lamination membrane-type cell.
Embodiment 2-13 to 2-16
Except using two (nine fluorine fourth sulphonyl) the imines lithiums (Compound D) of imide salt, with embodiment 2-1 to 2-4 in identical mode make the lamination membrane-type cell.
Embodiment 2-17 to 2-20
Except using imide salt perfluoropropane-1,3-disulfonyl imines lithium (compd E), with embodiment 2-1 to 2-4 in identical mode make the lamination membrane-type cell.
The battery assessment
(a) high temperature circulation test
(b) high temperature trickle charge test
(c) discharge capacitance after the high temperature trickle charge
About standard evaluation battery according to the method described in the embodiment 1.
Following table 3 shows result of the test.
Table 3
Figure BDA0000067554070000441
Table 3 (continuing)
Figure BDA0000067554070000451
Shown in table 3 the result confirmed, find to utilize according to imide salt of the present invention and heteropoly acid and improve high temperature circulation and the trickle charge characteristic that relates in the reaction at both positive and negative polarity place.The angle of the discharge capacity after high temperature circulation and the trickle charge, silicomolybdic acid or silico-tungstic acid are especially preferably as heteropoly acid.Compare with the phosphorus homologue, siliceous heteropoly acid is considered to produce more stable SEI and therefore provides higher protection to electrode.
7. other execution modes
Although the present invention is described about some execution mode and embodiment, the present invention is not limited to these execution modes and embodiment, and can carry out various modifications and application within the scope of the invention.
For example, although aforementioned embodiments and embodiment have described the battery of battery, cylindrical batteries and the rectangular battery structure of lamination membranous type, the present invention is not limited in these.For example, the present invention also can be applicable to other battery structures, comprises the battery of coin and button structure and the battery of lamination electrode structure, and effectively same in these battery structures.And the structure of rolled electrode unit is not limited to winding-structure, also can utilize various other structures, for example laminar structure and foldable structure.
The present invention comprise with on the June 18th, 2010 of relevant theme of disclosed theme in the Japanese priority patent application JP 2010-139690 that Japan Patent office submits to, its full content is incorporated into this is for reference.
It should be appreciated by those skilled in the art that according to design needs and other factors, can carry out various modifications, combination, sub-portfolio and distortion, as long as they are in the scope of claims and equivalent thereof.

Claims (12)

1. nonaqueous electrolyte comprises:
Nonaqueous solvents;
Electrolytic salt;
Imide salt; And
At least a in heteropoly acid and the heteropoly compound.
2. nonaqueous electrolyte according to claim 1, wherein, described imide salt comprise following formula (I) and (II) shown in compound at least a,
(C mF2 m+1SO 2)(C nF 2n+1SO 2)NLi ...(I)
Wherein, m and n are the integer more than 0,
Figure FDA0000067554060000011
Wherein, R represents the straight or branched perfluorinated alkylidene of 2 to 4 carbon atoms.
3. nonaqueous electrolyte according to claim 2, wherein, the content of described imide salt is below the above 1.0mol/kg of 0.01mol/kg.
4. nonaqueous electrolyte according to claim 1, wherein, described heteropoly acid and described heteropoly compound be by following formula (III), (IV), (V) with any one expression (VI),
Formula (III)
HxAy[BD 6O 24]·zH 2O
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤8,0≤y≤8 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0;
Formula (IV)
HxAy[BD 12O 40]·zH 2O
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤4,0≤y≤4 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0;
Formula (V)
HxAy[B 2D 18O 62]·zH 2O
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤8,0≤y≤8 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0;
Formula (VI)
HxAy[B 5D 30O 110]·zH 2O
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤15,0≤y≤15 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0.
5. nonaqueous electrolyte according to claim 4, wherein, the total content of described heteropoly acid and described heteropoly compound is below the above 3.0 weight % of 0.01 weight %.
6. nonaqueous electrolyte according to claim 1, wherein, described nonaqueous solvents comprise formula (VII) and (VIII) shown in cyclic carbonate at least a,
Wherein, R1 to R4 is hydrogen group, halogen group, alkyl or haloalkyl, and among the R1 to R4 at least one be halogen group or haloalkyl,
Figure FDA0000067554060000032
Wherein, R5 and R6 are hydrogen group or alkyl.
7. nonaqueous electrolyte according to claim 1, wherein, described electrolytic salt comprises lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4), lithium perchlorate (LiClO 4) and hexafluoroarsenate lithium (LiAsF 6) at least a.
8. nonaqueous electrolyte battery comprises:
Anodal;
Negative pole; And
Nonaqueous electrolyte,
Wherein, described positive pole comprises and comes from imide salt and be formed on coating at least a portion on described anodal surface, and
Wherein said negative pole is included in the gel coat that forms at least a portion of described negative terminal surface, described gel coat comes from least a in heteropoly acid and the heteropoly compound, and comprises noncrystal polyacid and/or the multi-acid salt compound that contains one or more multielements.
9. nonaqueous electrolyte battery according to claim 8, wherein, described imide salt comprise following formula (I) and (II) shown in compound at least a,
(C mF 2m+1SO 2)(C nF 2n+1SO 2)NLi ....(I)
Wherein, m and n are the integer more than 0,
Figure FDA0000067554060000041
Wherein, R represents the straight or branched perfluorinated alkylidene of 2 to 4 carbon atoms.
10. nonaqueous electrolyte battery according to claim 9, wherein, described heteropoly acid and heteropoly compound be by following formula (III), (IV), (V) with any one expression (VI),
Formula (III)
HxAy[BD 6O 24]·zH 2O
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤8,0≤y≤8 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0;
Formula (IV)
HxAy[BD 12O 40]·zH 2O
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), one or more elements in rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤4 respectively, 0≤y≤4 and 0≤z≤50, wherein at least one among x and the y is not 0;
Formula (V)
HxAy[B 2D 18O 62]·zH 2O
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤8,0≤y≤8 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0;
Formula (VI)
HxAy[B 5D 30O 110]·zH 2O
Wherein, A represents lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), magnesium (Mg), calcium (Ca), aluminium (Al), ammonium (NH 4), ammonium salt or microcosmic salt, B represents phosphorus (P), silicon (Si), arsenic (As) or germanium (Ge), D is one or more elements that are selected from titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), rhodium (Rh), cadmium (Cd), indium (In), tin (Sn), tantalum (Ta), tungsten (W), rhenium (Re) and the thallium (Tl), x, y and z satisfy 0≤x≤15,0≤y≤15 and 0≤z≤50 respectively, and wherein at least one among x and the y is not 0.
11. nonaqueous electrolyte battery according to claim 8, wherein, described nonaqueous solvents comprise following formula (VII) and (VIII) expression cyclic carbonate at least a,
Figure FDA0000067554060000061
Wherein, R1 to R4 is hydrogen group, halogen group, alkyl or haloalkyl, and among the R1 to R4 at least one be halogen group or haloalkyl,
Figure FDA0000067554060000062
Wherein, R5 and R6 are hydrogen group or alkyl.
12. nonaqueous electrolyte battery according to claim 8 further comprises by the film formed external member of lamination.
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Application publication date: 20111221